US5262461A - Polyarylene sulfide resin composition and method for preparing the same - Google Patents
Polyarylene sulfide resin composition and method for preparing the same Download PDFInfo
- Publication number
- US5262461A US5262461A US07/856,148 US85614892A US5262461A US 5262461 A US5262461 A US 5262461A US 85614892 A US85614892 A US 85614892A US 5262461 A US5262461 A US 5262461A
- Authority
- US
- United States
- Prior art keywords
- polyarylene sulfide
- component
- filler
- mixture
- sulfide resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229920000412 polyarylene Polymers 0.000 title claims abstract description 40
- 239000011342 resin composition Substances 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims description 30
- 229920005989 resin Polymers 0.000 claims abstract description 54
- 239000011347 resin Substances 0.000 claims abstract description 54
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- -1 silane compound Chemical class 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 238000004898 kneading Methods 0.000 claims abstract description 13
- 238000009835 boiling Methods 0.000 claims abstract description 8
- 229910000077 silane Inorganic materials 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 47
- 239000000945 filler Substances 0.000 claims description 19
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 16
- 238000002844 melting Methods 0.000 claims description 16
- 230000008018 melting Effects 0.000 claims description 16
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 16
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 14
- 239000003365 glass fiber Substances 0.000 claims description 14
- 229920001577 copolymer Polymers 0.000 claims description 13
- XWUCFAJNVTZRLE-UHFFFAOYSA-N 7-thiabicyclo[2.2.1]hepta-1,3,5-triene Chemical group C1=C(S2)C=CC2=C1 XWUCFAJNVTZRLE-UHFFFAOYSA-N 0.000 claims description 8
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 6
- 239000004917 carbon fiber Substances 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- SOHCOYTZIXDCCO-UHFFFAOYSA-N 6-thiabicyclo[3.1.1]hepta-1(7),2,4-triene Chemical group C=1C2=CC=CC=1S2 SOHCOYTZIXDCCO-UHFFFAOYSA-N 0.000 claims description 5
- 229920000299 Nylon 12 Polymers 0.000 claims description 5
- 229920002292 Nylon 6 Polymers 0.000 claims description 5
- 239000012765 fibrous filler Substances 0.000 claims description 4
- 229920001519 homopolymer Polymers 0.000 claims description 4
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 238000000465 moulding Methods 0.000 abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 14
- 230000000704 physical effect Effects 0.000 description 12
- 229920000642 polymer Polymers 0.000 description 12
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 9
- 239000000835 fiber Substances 0.000 description 9
- 239000004952 Polyamide Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 229920002647 polyamide Polymers 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 150000001298 alcohols Chemical class 0.000 description 7
- 125000000732 arylene group Chemical group 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229920005992 thermoplastic resin Polymers 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 4
- 239000000806 elastomer Substances 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000011369 resultant mixture Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 3
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 239000011256 inorganic filler Substances 0.000 description 3
- 229910003475 inorganic filler Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 description 3
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- 229930182556 Polyacetal Natural products 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 229920000578 graft copolymer Polymers 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 2
- 229920001707 polybutylene terephthalate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229920006324 polyoxymethylene Polymers 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- TYFQFVWCELRYAO-UHFFFAOYSA-N suberic acid Chemical compound OC(=O)CCCCCCC(O)=O TYFQFVWCELRYAO-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 125000000101 thioether group Chemical group 0.000 description 2
- ORTVZLZNOYNASJ-UPHRSURJSA-N (z)-but-2-ene-1,4-diol Chemical compound OC\C=C/CO ORTVZLZNOYNASJ-UPHRSURJSA-N 0.000 description 1
- 125000002030 1,2-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([*:2])C([H])=C1[H] 0.000 description 1
- 125000001989 1,3-phenylene group Chemical group [H]C1=C([H])C([*:1])=C([H])C([*:2])=C1[H] 0.000 description 1
- GVNHOISKXMSMPX-UHFFFAOYSA-N 2-[butyl(2-hydroxyethyl)amino]ethanol Chemical compound CCCCN(CCO)CCO GVNHOISKXMSMPX-UHFFFAOYSA-N 0.000 description 1
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 description 1
- VJAVYPBHLPJLSN-UHFFFAOYSA-N 3-dimethoxysilylpropan-1-amine Chemical compound CO[SiH](OC)CCCN VJAVYPBHLPJLSN-UHFFFAOYSA-N 0.000 description 1
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 1
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000572 Nylon 6/12 Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
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- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
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- 235000019445 benzyl alcohol Nutrition 0.000 description 1
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- 239000010951 brass Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920006147 copolyamide elastomer Polymers 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- INSRQEMEVAMETL-UHFFFAOYSA-N decane-1,1-diol Chemical compound CCCCCCCCCC(O)O INSRQEMEVAMETL-UHFFFAOYSA-N 0.000 description 1
- YQLZOAVZWJBZSY-UHFFFAOYSA-N decane-1,10-diamine Chemical compound NCCCCCCCCCCN YQLZOAVZWJBZSY-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
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- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
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- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
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- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
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- 239000006082 mold release agent Substances 0.000 description 1
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- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
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- OEIJHBUUFURJLI-UHFFFAOYSA-N octane-1,8-diol Chemical compound OCCCCCCCCO OEIJHBUUFURJLI-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
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- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000005650 substituted phenylene group Chemical group 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/02—Polythioethers; Polythioether-ethers
Definitions
- the present invention relates to an improved polyarylene sulfide resin composition and a method of preparing the same.
- the present invention relates to a polyarylene sulfide resin composition having excellent impact resistance and heat resistance and which is produced by blending specific amounts of alkoxysilane compound, water and the like to a resin component comprising a polyarylene sulfide resin and a polyamide resin, and heat melting and kneading the resultant blend, and to the method of preparing same.
- thermoplastic resin having high heat and chemical resistance and excellent flame retardance has been demanded as the material of construction for the components of electrical or electronic appliances, automobile devices or chemical instruments.
- Polyarylene sulfide resin represented by polyphenylene sulfide, is one of the resins satisfying this demand and is inexpensive relative to the excellent properties thereof, such that the demand for polyarylene sulfide resin has increased.
- polyarylene sulfide resin has critical disadvantages in that it is inferior to other engineering plastics such as nylon, polycarbonate, polyacetal, polybutylene terephthalate, and the like, because polyarylene sulfide resin has poor ductility and is therefore brittle.
- the present inventors have made thorough investigations of polyarylene sulfide resin compositions having high toughness and impact resistance and the method for preparing the same, and examined a reactive substance capable of reacting with both polyarylene sulfide resin and polyamide resin. Consequently, it has been found that a silane compound having a alkoxysilane group within the molecule thereof provides an improvement in impact strength of the blend.
- the inventors have applied for patents as Japanese Patent Laid-open Nos. 320140/1989, 44140/1990 and 110839/1990 on such composition and the method for preparing same.
- the improved blend realizes good toughness and impact strength, but the physical properties thereof may vary occasionally. Accordingly improvement has been desired.
- the present inventors have found that to stably produce a polyarylene sulfide resin composition with still more improved toughness and impact strength, the presence of water and the like is influential. Accordingly blending an alkoxysilane compound and a specific amount of water or alcohols with a boiling point of 100° C. or more, with a blend of polyarylene sulfide resin and polyamide resin, and processing and kneading the resultant blend at a specific temperature for a specific period of time, a molding material with remarkably high toughness and utility can be produced in a stable fashion.
- the present invention therefore relates to a method of preparing a polyarylene sulfide resin composition, comprising mixing (C) 0.01 to 5 parts by weight of at least one silane compound selected from the group consisting of vinylalkoxysilane, epoxyalkoxysilane, aminoalkoxysilane, mercaptoalkoxysilane and allylalkoxysilane, and (D) 0.03 to 5 moles per mole of the component (C) of water, or at least one alcohol selected from alcohols with a boiling point of 100° C.
- silane compound selected from the group consisting of vinylalkoxysilane, epoxyalkoxysilane, aminoalkoxysilane, mercaptoalkoxysilane and allylalkoxysilane
- D 0.03 to 5 moles per mole of the component (C) of water, or at least one alcohol selected from alcohols with a boiling point of 100° C.
- a resin component comprising (A) 97 to 20 parts by weight of a polyarylene sulfide resin and (B) 3 to 80 parts by weight of a polyamide resin, and processing the resultant mixture by heat melting and kneading in the presence of at least the above four components for 30 seconds or more, and relates to a resin composition produced according to the method for preparing the same.
- the polyarylene sulfide resin as the component (A) to be used in the present invention is constituted mainly of repeating units -(Ar-S)- (provided that Ar is arylene group).
- arylene group there can be used p-phenylene group, m-phenylene group, o-phenylene group, substituted phenylene groups (provided that the substituent is an alkyl group, preferably an alkyl group of C 1 to C 5 or a phenylene group), p,p'-diphenylene sulfone group, p,p'-biphenylene group, p,p'-diphenylene ether group, p,p'-diphenylene carbonyl group, naphthalene group and the like.
- a polymer employing an identical repeating unit among the arylene sulfide group constituted of the arylene groups described above, namely a homopolymer.
- a copolymer containing different repeating units may be preferable in some cases.
- the copolymer there can be used a combination of two or more different arylene sulfide groups comprising the arylene group described above, but in particular a combination of p-phenylene sulfide groups in the main and containing m-phenylene sulfide groups is preferably used.
- substantially linear ones containing 60 mole % or more, more preferably 70 mole % or more of p-phenylene sulfide groups are suitable from the standpoint of physical properties such as heat resistance, moldability and mechanical properties.
- copolymers containing 5 to 40 mole %, in particular 10 to 25 mole % of m-phenylene sulfide group are preferable as the copolymer.
- those copolymers containing component-repeating units in block form (for example, those described in Japanese Patent Laid-open No. 14228/1986) rather than in a random form can be used favorably, because of good processability and excellent heat resistance and mechanical properties thereof.
- the polyarylene sulfide resin as component (A) to be used in the present invention there can be employed a polymer with the molding processability improved by crosslinking the polymer described above oxidatively or thermally whereby its melt viscosity is increased.
- a polymer having a substantially linear structure obtained by polycondensation of principally bifunctional monomers. In many cases, the latter polymer having a substantially linear structure is superior with respect to the physical properties of the molded articles thus obtained.
- polyarylene sulfide resin of the present invention there can preferably be used, other than the polymers described above, a resin prepared by blending with the linear polymer described above a crosslinked polyarylene sulfide resin prepared by using and polymerizing monomers with three or more functional groups in combination as a part of the monomer.
- the polyamide resin useful as component (B) of the present invention includes various known polyamide resins. These include for example, polyamide resins obtained by polycondensing dicarboxylic acid such as oxalic acid, adipic acid, suberic acid, sebacic acid, terephthalic acid, isophthalic acid, and 1,4-cyclohexyl dicarboxylic acid, with diamine such as ethylene diamine, pentamethylene diamine, hexamethylene diamine, decamethylene diamine, 1,4-cyclohexyl diamine and m-xylylene diamine; polyamide resins obtained by polymerizing cyclic lactam such as caprolactam and lauric lactam; polyamide resins obtained by copolymerizing cyclic lactam and the salts of dicarboxylic acid and diamine or the like. Among these polyamide resins, nylon 6, nylon 66, nylon 12, the copolymers thereof and the like are illustrated preferably.
- polyamide elastomer resins can be used as the polyamide resin as the component (B).
- Polyamide elastomer resins are polyamide block copolymers having a bending modulus of 10,000 kgf/cm 2 or less (relative humidity of 50% and 23° C.) composed of polyamide hard segments bonded with other soft segments.
- soft segments of such elastomer polyalkylene oxide (the alkylene group having 2 to 6 carbon atoms) is a representative example.
- a great number of reports have been made about the synthesis of such polyamide elastomers, and the synthesis is commonly carried out in two stages i.e., the production of nylon oligomer and the polymerization thereof by esterification.
- the polyamide component as the hard segment herein includes the polyamides such as polyamide 6, polyamide 66, polyamide 6,12, polyamide 11, polyamide 12 and the like;
- the polyether component as the soft segment includes polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol and the like.
- polyamide resin as the component (B) is not limited to one type, as two or more types may be used in combination in order to control the physical properties.
- the mixing amount of polyamide resin (B) is 3 to 80% by weight to the total amount of the components (A) and (B). If the component (B) is much less, a lower effect is obtained with respect to toughness improvement; if too much, the advantage of the polyarylene sulfide resin (A) is deteriorated.
- the present invention is characterized by adding and mixing the alkoxysilane compound (C) along with the above resin components.
- the alkoxysilane (C) to be used in the present invention is selected from one or more of vinylalkoxysilane, epoxyalkoxysilane, aminoalkoxysilane, mercaptoalkoxysilane, allylalkoxysilane, etc.
- vinylalkoxysilane examples include vinyltriethoxysilane, vinyltrimethoxysilane, and vinyltris( ⁇ -methoxyethoxy)silane, etc.
- epoxyalkoxysilane examples include ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and ⁇ -glycidoxypropyltriethoxysilane, etc.
- aminoalkoxysilane examples include ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyldimethoxysilane, ⁇ -aminopropylmethyldiethoxysilane, N-( ⁇ -aminoethyl)- ⁇ -aminopropyltrimethoxysilane, N-phenyl- ⁇ -aminopropyltrimethoxysilane, etc.
- Examples of mercaptoalkoxysilane include ⁇ -mercaptopropyltrimethoxysilane, ⁇ -mercaptopropyltriethoxysilane, etc.
- allylalkoxysilane examples include ⁇ -diallylaminopropyltrimethoxysilane, ⁇ -allylaminopropyltrimethoxysilane, ⁇ -allylthiopropylltrimethoxysilane, etc..
- the amount of the alkoxysilane compound to be used as the component (C) is 0.01 to 5 parts by weight, preferably 0.1 to 3 parts by weight to 100 parts by weight of the total amount of polyarylene sulfide resin [component (A)] and polyamide resin [component (B)].
- the amount of alkoxysilane compound to be added varies depending on the type thereof and the use of the objective compositions. If too little is used, a lower effect is obtained on toughness improvement; if too much, the melt viscosity increased excessively causing disadvantages during mold processing.
- the present invention is characterized in that a controlled amount of water or alcohols with a boiling point of 100° C. or more, as component (D), are added along with components (A), (B) and (C), and the mixture heat melted and kneaded.
- a controlled amount of water or alcohols with a boiling point of 100° C. or more, as component (D) are added along with components (A), (B) and (C), and the mixture heat melted and kneaded.
- component (D) a controlled amount of water or alcohols with a boiling point of 100° C. or more, as component (D)
- component (D) to be used in the present invention include for example isobutyl alcohol, isopentyl alcohol, cyclohexanol, benzyl alcohol, ethylene glycol, propylene glycol, butanediol, pentanediol, neopentyl glycol, hexanediol, octanediol, decanediol, glycerine, diethylene glycol, triethylene glycol, pentaerythritol, clohexanedimethanol, hydroquinone, N-ethyl-2,2'-iminodiethanol, N-butyl-2,2'-iminodiethanol, 2-butyl 1,4-diol, 2-butene 1,4-diol, bisphenol A, 2,2'-bis(4-hydroxyethoxyphenyl)propane, xylene glycol, etc.
- the amount of the component (D) to be used varies, depending on the type, the preparative method of the compositions and the objective physical properties of the compositions. Problems may arise concerning the stable production of compositions with good toughness if the amount of component (D) added is too small; whereas disadvantages may be caused by the occurrence of bleedout on the surface of molded articles if the amount is too much. Further, the preferable amount of the component (D) to be used will vary depending on the mode as to how the component is added and blended.
- component (D) in the case in which component (D) is preliminarily added to the alkoxysilane compound (C) and then kneaded with other components, a relatively small amount is generally preferable within the range described above. In the case in which component (D) is added and blended in the state of being adsorbed onto other components (or being humidified), a relatively greater amount may be appropriate.
- component (D) may be added to any one of the components (A), (B), and (C), and the component (E) in some cases. It is particularly preferable to preliminarily add component (D) to the alkoxysilane compound (C).
- alcohols with a boiling point of 100° C. or more as the component (D) it has been observed that alcohols with two or more hydroxyl groups within the individual molecule rather than those with one hydroxyl group within the individual molecules tend to exert the beneficial effects using a smaller amount thereof.
- the composition of the present invention can be blended with an inorganic filler, as the component (E).
- an inorganic filler as the component (E).
- such filler (E) is blended in order to produce molded articles having excellent properties such as mechanical strength, heat resistance, dimensional stability, electrical properties and the like.
- Fibrous, powdery and flaky fillers are used as the filler (E), depending on the object.
- fibrous fillers there are included inorganic fibrous materials such as glass fiber, asbestos fiber, carbon fiber, silica fiber, silica/alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber and potassium titanate fiber, and fibers of metals including stainless steel, aluminum, titanium, copper or brass.
- Particularly representative fibrous fillers are glass fiber or carbon fiber.
- organic fibrous materials with high melting points may also be used, including polyamides, fluororesins, alkali resins and the like.
- the powdery filler includes carbon black, silica, quartz powder, glass bead, glass powder, silicates such as calcium silicate, aluminum silicate, kaolin, talc, clay, diastomaceous earth and wollastonite, metal oxides such as iron oxide, titanium oxide and alumina; metal carbonates such as calcium carbonate and magnesium carbonate; metal sulfates such as calcium sulfate and barium sulfate; silicon carbide, silicon nitride, boron nitride and various metal powders.
- silicates such as calcium silicate, aluminum silicate, kaolin, talc, clay, diastomaceous earth and wollastonite
- metal oxides such as iron oxide, titanium oxide and alumina
- metal carbonates such as calcium carbonate and magnesium carbonate
- metal sulfates such as calcium sulfate and barium sulfate
- silicon carbide silicon nitride, boron nitride and various metal
- the flaky filler includes mica, glass flake and various metal foils.
- inorganic fillers may be used alone or in combination of two or more thereof.
- a fibrous filler in particular glass or carbon fiber, with a powdery or flaky filler is preferable as a combination with respect to the provision of mechanical strength, dimensional precision and electrical properties.
- the amount of inorganic filler to be added is 400 parts by weight or less per 100 parts by weight of the total amount of the resin components (A) and (B). If the amount of filler exceeds this, the processability during molding and toughness are deteriorated unfavorably. It is specifically preferable to add 250 parts by weight or less of filler per 100 parts by weight of (A) and (B).
- thermoplastic resins herein used may be any thermoplastic resin stable at a high temperature approximately of the melting temperature of a polyarylene sulfide resin.
- olefin polymer aromatic polyester polymer comprising aromatic dicarboxylic acid such as polyethylene terephthalate, polybutylene terephthalate, complete aromatic polyester, etc. and diol or oxycarboxylic acid, polycarbonate, ABS, polyphenylene oxide, polyalkylacrylate, polyacetal, polysulfone, polyether sulfone, polyether imide, polyether ketone, fluororesin, etc.
- these thermoplastic resins may be used in combination of two or more thereof.
- ethylene copolymer or its graft copolymer as polyolefin polymer for example, copolymer of ethylene and ⁇ , ⁇ -unsaturated fatty acid or alkyl ester or glycidyl ester thereof, and the graft copolymer produced by further grafting vinyl polymer with the copolymer, and the like, are specifically preferable as an auxiliary component.
- composition of the present invention can be prepared by known methods, but it is required to mix and knead simultaneously at least the four components (A), (B), (C) and (D) at the heat melted state thereof for 30 seconds or more.
- the component (D) is preliminarily added to the component (C), and the resulting mixture is blended with the components (A) and (B), and (E) if necessary, which is then preliminarily mixed uniformly with a mixer such as a tumbler or a Henschel mixer.
- the resultant mixture is then fed to a uniaxial or biaxial extruder for heat melting and kneading, to be prepared as pellets.
- the components (A), (B), (C) and (D) may be directly mixed, without preliminarily adding the component (D) to the component (C); or the component (D) may be preliminarily adsorbed onto the component (A) or (B), which is then mixed with the component (C). In this latter case, the tendency is that a greater amount of component (D) is needed, compared with the amount of component (D) in case in which component (D) is preliminarily added to component (C).
- the form of the components (A) and (B) may be pellets, but a part of the component (A) or (B) or its entirety is preferably made into powder.
- a mixture of (C) and (D) is added to the part of the powder, or (C) and (D) are added separately to the part of the powder.
- the resultant mixture is uniformly mixed once with a blender, which is then uniformly mixed with the remaining components for the process of heat melting and kneading.
- the component (E) may be added during or after the process of heat melting and kneading.
- the temperature for the process of heat melting and kneading is higher by 5° C. to 100° C. than the melting point of the resin component, and is preferably higher by 10° C. to 60° C. than the resin melting point. At temperatures too high, the degradation of the resin and abnormal reactions may unfavorably result. Further, the period of time for heat melting and kneading varies depending on the temperature of the processing and the types and amounts of components (C) and (D) added. The time for heat melting and kneading is at least 30 seconds or more and 15 minutes or less, and preferably 1 to 10 minutes.
- antioxidants there may be added antioxidants, heat stabilizers, lubricants, nucleating agents, ultraviolet absorbers, colorants, mold release agents, and other common additives, within a range without deviating from the objects of the present invention.
- the polyarylene sulfide resin composition of the present invention has the following effects;
- Molded articles with good mechanical properties such as tensile elongation, impact strength, etc. are produced in a stable fashion;
- Example 2 Replacing the water in Example 2 and Comparative Example 2 with benzyl alcohol, ethylene glycol, butanediol and glycerin, tests were performed at the blend ratios shown in Table 6, as in Example 2 and Comparative Example 2. The results are shown in Table 6.
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Abstract
PCT No. PCT/JP91/01090 Sec. 371 Date Mar. 30, 1992 Sec. 102(e) Date Mar. 30, 1992 PCT Filed Aug. 15, 1991 PCT Pub. No. WO92/03508 PCT Pub. Date Mar. 5, 1992.A polyarylene sulfide resin composition useful for molding articles is obtained by mixing and melt kneading a polyarylene sulfide resin, a polyamide resin, a silane compound and either water or an alcohol having a boiling point of at least 100 DEG C.
Description
The present invention relates to an improved polyarylene sulfide resin composition and a method of preparing the same.
More particularly, the present invention relates to a polyarylene sulfide resin composition having excellent impact resistance and heat resistance and which is produced by blending specific amounts of alkoxysilane compound, water and the like to a resin component comprising a polyarylene sulfide resin and a polyamide resin, and heat melting and kneading the resultant blend, and to the method of preparing same.
Recently, a thermoplastic resin having high heat and chemical resistance and excellent flame retardance has been demanded as the material of construction for the components of electrical or electronic appliances, automobile devices or chemical instruments.
Polyarylene sulfide resin, represented by polyphenylene sulfide, is one of the resins satisfying this demand and is inexpensive relative to the excellent properties thereof, such that the demand for polyarylene sulfide resin has increased. However, polyarylene sulfide resin has critical disadvantages in that it is inferior to other engineering plastics such as nylon, polycarbonate, polyacetal, polybutylene terephthalate, and the like, because polyarylene sulfide resin has poor ductility and is therefore brittle.
As a means for overcoming these problems, it is known that blending a fibrous reinforcement material such as glass fiber or carbon fiber and other fillers improves the properties of polyarylene sulfide resin such as strength, rigidity, toughness, heat resistance and the like. However, even by blending such reinforcement materials with polyarylene sulfide resin, the resin still has poor toughness compared with the engineering plastics described above, and the application polyarylene sulfide resin for a great number of uses may be limited in some cases, even though the resin has excellent chemical resistance, heat resistance and nonflammability.
The present inventors have made thorough investigations of polyarylene sulfide resin compositions having high toughness and impact resistance and the method for preparing the same, and examined a reactive substance capable of reacting with both polyarylene sulfide resin and polyamide resin. Consequently, it has been found that a silane compound having a alkoxysilane group within the molecule thereof provides an improvement in impact strength of the blend. The inventors have applied for patents as Japanese Patent Laid-open Nos. 320140/1989, 44140/1990 and 110839/1990 on such composition and the method for preparing same. The improved blend realizes good toughness and impact strength, but the physical properties thereof may vary occasionally. Accordingly improvement has been desired.
The present inventors have found that to stably produce a polyarylene sulfide resin composition with still more improved toughness and impact strength, the presence of water and the like is influential. Accordingly blending an alkoxysilane compound and a specific amount of water or alcohols with a boiling point of 100° C. or more, with a blend of polyarylene sulfide resin and polyamide resin, and processing and kneading the resultant blend at a specific temperature for a specific period of time, a molding material with remarkably high toughness and utility can be produced in a stable fashion. The present invention therefore relates to a method of preparing a polyarylene sulfide resin composition, comprising mixing (C) 0.01 to 5 parts by weight of at least one silane compound selected from the group consisting of vinylalkoxysilane, epoxyalkoxysilane, aminoalkoxysilane, mercaptoalkoxysilane and allylalkoxysilane, and (D) 0.03 to 5 moles per mole of the component (C) of water, or at least one alcohol selected from alcohols with a boiling point of 100° C. or more, or a mixture thereof, with 100 parts by weight of a resin component comprising (A) 97 to 20 parts by weight of a polyarylene sulfide resin and (B) 3 to 80 parts by weight of a polyamide resin, and processing the resultant mixture by heat melting and kneading in the presence of at least the above four components for 30 seconds or more, and relates to a resin composition produced according to the method for preparing the same.
The polyarylene sulfide resin as the component (A) to be used in the present invention is constituted mainly of repeating units -(Ar-S)- (provided that Ar is arylene group).
As the arylene group, there can be used p-phenylene group, m-phenylene group, o-phenylene group, substituted phenylene groups (provided that the substituent is an alkyl group, preferably an alkyl group of C1 to C5 or a phenylene group), p,p'-diphenylene sulfone group, p,p'-biphenylene group, p,p'-diphenylene ether group, p,p'-diphenylene carbonyl group, naphthalene group and the like.
In this invention, there can be used a polymer employing an identical repeating unit among the arylene sulfide group constituted of the arylene groups described above, namely a homopolymer. A copolymer containing different repeating units may be preferable in some cases.
As the homopolymer, a substantially linear one with p-phenylene sulfide group as the repeating unit and in which p-phenylene group is employed as the arylene group, is perferably used.
As the copolymer, there can be used a combination of two or more different arylene sulfide groups comprising the arylene group described above, but in particular a combination of p-phenylene sulfide groups in the main and containing m-phenylene sulfide groups is preferably used. Among copolymers, substantially linear ones containing 60 mole % or more, more preferably 70 mole % or more of p-phenylene sulfide groups, are suitable from the standpoint of physical properties such as heat resistance, moldability and mechanical properties.
Further, copolymers containing 5 to 40 mole %, in particular 10 to 25 mole % of m-phenylene sulfide group are preferable as the copolymer.
In this invention, those copolymers containing component-repeating units in block form (for example, those described in Japanese Patent Laid-open No. 14228/1986) rather than in a random form can be used favorably, because of good processability and excellent heat resistance and mechanical properties thereof.
The polyarylene sulfide resin as component (A) to be used in the present invention, there can be employed a polymer with the molding processability improved by crosslinking the polymer described above oxidatively or thermally whereby its melt viscosity is increased. There can also be used a polymer having a substantially linear structure, obtained by polycondensation of principally bifunctional monomers. In many cases, the latter polymer having a substantially linear structure is superior with respect to the physical properties of the molded articles thus obtained.
As the polyarylene sulfide resin of the present invention, there can preferably be used, other than the polymers described above, a resin prepared by blending with the linear polymer described above a crosslinked polyarylene sulfide resin prepared by using and polymerizing monomers with three or more functional groups in combination as a part of the monomer.
The polyamide resin useful as component (B) of the present invention includes various known polyamide resins. These include for example, polyamide resins obtained by polycondensing dicarboxylic acid such as oxalic acid, adipic acid, suberic acid, sebacic acid, terephthalic acid, isophthalic acid, and 1,4-cyclohexyl dicarboxylic acid, with diamine such as ethylene diamine, pentamethylene diamine, hexamethylene diamine, decamethylene diamine, 1,4-cyclohexyl diamine and m-xylylene diamine; polyamide resins obtained by polymerizing cyclic lactam such as caprolactam and lauric lactam; polyamide resins obtained by copolymerizing cyclic lactam and the salts of dicarboxylic acid and diamine or the like. Among these polyamide resins, nylon 6, nylon 66, nylon 12, the copolymers thereof and the like are illustrated preferably.
Also, polyamide elastomer resins can be used as the polyamide resin as the component (B). Polyamide elastomer resins are polyamide block copolymers having a bending modulus of 10,000 kgf/cm2 or less (relative humidity of 50% and 23° C.) composed of polyamide hard segments bonded with other soft segments. As the soft segments of such elastomer, polyalkylene oxide (the alkylene group having 2 to 6 carbon atoms) is a representative example. A great number of reports have been made about the synthesis of such polyamide elastomers, and the synthesis is commonly carried out in two stages i.e., the production of nylon oligomer and the polymerization thereof by esterification. The polyamide component as the hard segment herein includes the polyamides such as polyamide 6, polyamide 66, polyamide 6,12, polyamide 11, polyamide 12 and the like; the polyether component as the soft segment includes polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol and the like.
Furthermore, the polyamide resin as the component (B) is not limited to one type, as two or more types may be used in combination in order to control the physical properties.
In accordance with the present invention, the mixing amount of polyamide resin (B) is 3 to 80% by weight to the total amount of the components (A) and (B). If the component (B) is much less, a lower effect is obtained with respect to toughness improvement; if too much, the advantage of the polyarylene sulfide resin (A) is deteriorated.
The present invention is characterized by adding and mixing the alkoxysilane compound (C) along with the above resin components.
The alkoxysilane (C) to be used in the present invention is selected from one or more of vinylalkoxysilane, epoxyalkoxysilane, aminoalkoxysilane, mercaptoalkoxysilane, allylalkoxysilane, etc.
Examples of vinylalkoxysilane include vinyltriethoxysilane, vinyltrimethoxysilane, and vinyltris(β-methoxyethoxy)silane, etc.
Examples of epoxyalkoxysilane include γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and γ-glycidoxypropyltriethoxysilane, etc.
Examples of aminoalkoxysilane include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, etc.
Examples of mercaptoalkoxysilane include γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, etc.
Examples of allylalkoxysilane include γ-diallylaminopropyltrimethoxysilane, γ-allylaminopropyltrimethoxysilane, γ-allylthiopropylltrimethoxysilane, etc..
The amount of the alkoxysilane compound to be used as the component (C) is 0.01 to 5 parts by weight, preferably 0.1 to 3 parts by weight to 100 parts by weight of the total amount of polyarylene sulfide resin [component (A)] and polyamide resin [component (B)].
The amount of alkoxysilane compound to be added varies depending on the type thereof and the use of the objective compositions. If too little is used, a lower effect is obtained on toughness improvement; if too much, the melt viscosity increased excessively causing disadvantages during mold processing.
The present invention is characterized in that a controlled amount of water or alcohols with a boiling point of 100° C. or more, as component (D), are added along with components (A), (B) and (C), and the mixture heat melted and kneaded. Unfavorably, alcohols with a boiling point of 100° C. or less vaporize during the heat melting process, so their effect may not be sufficiently exhibited. The alcohols with a boiling point of 100° C. or more belonging to component (D) to be used in the present invention, include for example isobutyl alcohol, isopentyl alcohol, cyclohexanol, benzyl alcohol, ethylene glycol, propylene glycol, butanediol, pentanediol, neopentyl glycol, hexanediol, octanediol, decanediol, glycerine, diethylene glycol, triethylene glycol, pentaerythritol, clohexanedimethanol, hydroquinone, N-ethyl-2,2'-iminodiethanol, N-butyl-2,2'-iminodiethanol, 2-butyl 1,4-diol, 2-butene 1,4-diol, bisphenol A, 2,2'-bis(4-hydroxyethoxyphenyl)propane, xylene glycol, etc..
It is required to regulate the amount of the component (D) to be used within a range of 0.03 to 5 mole, preferably 0.03 to 3 mole, per one mole of the component (C). The amount of the component (D) to be added varies, depending on the type, the preparative method of the compositions and the objective physical properties of the compositions. Problems may arise concerning the stable production of compositions with good toughness if the amount of component (D) added is too small; whereas disadvantages may be caused by the occurrence of bleedout on the surface of molded articles if the amount is too much. Further, the preferable amount of the component (D) to be used will vary depending on the mode as to how the component is added and blended. In other words, in the case in which component (D) is preliminarily added to the alkoxysilane compound (C) and then kneaded with other components, a relatively small amount is generally preferable within the range described above. In the case in which component (D) is added and blended in the state of being adsorbed onto other components (or being humidified), a relatively greater amount may be appropriate. Regarding the method as to how to add component (D), component (D) may be added to any one of the components (A), (B), and (C), and the component (E) in some cases. It is particularly preferable to preliminarily add component (D) to the alkoxysilane compound (C). Also, in case of using alcohols with a boiling point of 100° C. or more as the component (D), it has been observed that alcohols with two or more hydroxyl groups within the individual molecule rather than those with one hydroxyl group within the individual molecules tend to exert the beneficial effects using a smaller amount thereof.
Other than the components described above, the composition of the present invention can be blended with an inorganic filler, as the component (E). Preferably, such filler (E) is blended in order to produce molded articles having excellent properties such as mechanical strength, heat resistance, dimensional stability, electrical properties and the like. Fibrous, powdery and flaky fillers are used as the filler (E), depending on the object.
As fibrous fillers, there are included inorganic fibrous materials such as glass fiber, asbestos fiber, carbon fiber, silica fiber, silica/alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber and potassium titanate fiber, and fibers of metals including stainless steel, aluminum, titanium, copper or brass. Particularly representative fibrous fillers are glass fiber or carbon fiber. Further, organic fibrous materials with high melting points may also be used, including polyamides, fluororesins, alkali resins and the like.
Alternatively, the powdery filler includes carbon black, silica, quartz powder, glass bead, glass powder, silicates such as calcium silicate, aluminum silicate, kaolin, talc, clay, diastomaceous earth and wollastonite, metal oxides such as iron oxide, titanium oxide and alumina; metal carbonates such as calcium carbonate and magnesium carbonate; metal sulfates such as calcium sulfate and barium sulfate; silicon carbide, silicon nitride, boron nitride and various metal powders.
The flaky filler includes mica, glass flake and various metal foils.
These inorganic fillers may be used alone or in combination of two or more thereof. The concurrent use of a fibrous filler, in particular glass or carbon fiber, with a powdery or flaky filler is preferable as a combination with respect to the provision of mechanical strength, dimensional precision and electrical properties.
The amount of inorganic filler to be added is 400 parts by weight or less per 100 parts by weight of the total amount of the resin components (A) and (B). If the amount of filler exceeds this, the processability during molding and toughness are deteriorated unfavorably. It is specifically preferable to add 250 parts by weight or less of filler per 100 parts by weight of (A) and (B).
To the composition of the present invention herein can be added as a supplement a small amount of other thermoplastic resins within a range without damaging the objects of the present invention, in addition to a polyarylene sulfide resin and a polyamide resin. The thermoplastic resins herein used may be any thermoplastic resin stable at a high temperature approximately of the melting temperature of a polyarylene sulfide resin.
For example, there are illustrated olefin polymer, aromatic polyester polymer comprising aromatic dicarboxylic acid such as polyethylene terephthalate, polybutylene terephthalate, complete aromatic polyester, etc. and diol or oxycarboxylic acid, polycarbonate, ABS, polyphenylene oxide, polyalkylacrylate, polyacetal, polysulfone, polyether sulfone, polyether imide, polyether ketone, fluororesin, etc.. Furthermore, these thermoplastic resins may be used in combination of two or more thereof. Among them, ethylene copolymer or its graft copolymer as polyolefin polymer, for example, copolymer of ethylene and α,β-unsaturated fatty acid or alkyl ester or glycidyl ester thereof, and the graft copolymer produced by further grafting vinyl polymer with the copolymer, and the like, are specifically preferable as an auxiliary component.
The composition of the present invention can be prepared by known methods, but it is required to mix and knead simultaneously at least the four components (A), (B), (C) and (D) at the heat melted state thereof for 30 seconds or more. Generally, the component (D) is preliminarily added to the component (C), and the resulting mixture is blended with the components (A) and (B), and (E) if necessary, which is then preliminarily mixed uniformly with a mixer such as a tumbler or a Henschel mixer. The resultant mixture is then fed to a uniaxial or biaxial extruder for heat melting and kneading, to be prepared as pellets. The components (A), (B), (C) and (D) may be directly mixed, without preliminarily adding the component (D) to the component (C); or the component (D) may be preliminarily adsorbed onto the component (A) or (B), which is then mixed with the component (C). In this latter case, the tendency is that a greater amount of component (D) is needed, compared with the amount of component (D) in case in which component (D) is preliminarily added to component (C). Furthermore, the form of the components (A) and (B) may be pellets, but a part of the component (A) or (B) or its entirety is preferably made into powder. Preferably, a mixture of (C) and (D) is added to the part of the powder, or (C) and (D) are added separately to the part of the powder. The resultant mixture is uniformly mixed once with a blender, which is then uniformly mixed with the remaining components for the process of heat melting and kneading. Also, the component (E) may be added during or after the process of heat melting and kneading.
The temperature for the process of heat melting and kneading is higher by 5° C. to 100° C. than the melting point of the resin component, and is preferably higher by 10° C. to 60° C. than the resin melting point. At temperatures too high, the degradation of the resin and abnormal reactions may unfavorably result. Further, the period of time for heat melting and kneading varies depending on the temperature of the processing and the types and amounts of components (C) and (D) added. The time for heat melting and kneading is at least 30 seconds or more and 15 minutes or less, and preferably 1 to 10 minutes.
The detailed mechanism of the actions and effects between the alkoxysilane compound component (C) and component (D) of the present invention has not yet thoroughly elucidated, but it is believed that the polyarylene sulfide molecule and polyamide molecule are efficiently bonded together via the presence of component (D), to improve the compatibility between the components (A) and (B). This is confirmed by electron microscopic observation of the cross section of a molded article from the composition. That is, in case of components (A) and (B) solely, the dispersion components are present as coarse particles (for example, 10 μ or less). According to the method of the present invention, it is observed that the dispersion components are in dispersion as extremely uniform and fine particles (at most 3μ or less, and generally 1μ or less).
Furthermore, there may be added antioxidants, heat stabilizers, lubricants, nucleating agents, ultraviolet absorbers, colorants, mold release agents, and other common additives, within a range without deviating from the objects of the present invention.
These additives may be added and blended, simultaneously with or separately from the process of heat melting and kneading. Effects of the Invention
The polyarylene sulfide resin composition of the present invention has the following effects;
(1) Molded articles with good mechanical properties such as tensile elongation, impact strength, etc. are produced in a stable fashion;
(2) The balance between the heat resistance and the mechanical properties is maintained at a higher degree.
The present invention will now be explained more concretely in the following examples, but the present invention is not intended to be limited solely to the embodiments shown therein.
Water was added to γ-aminopropyltriethoxysilane at the ratios shown in Table 1, with subsequent blending of polyphenylene sulfide polymer (a melting point of 285° C., a melt viscosity of 500 poise as measured at 310° C. and a shear rate of 1200 sec-1), and nylon 66, and in some cases glass fiber (chopped strand of 10 μm diameter and 3 mm in length), at the ratios shown in Table 1, which were then preliminarily mixed together for five minutes. The resultant mixture was heat melted and kneaded in an extruder at 310° C. (residence time of about 3 minutes) to produce pellets of polyphenylene sulfide resin composition.
Then, 10 ASTM test pieces were individually molded at the conditions of a cylinder temperature of 310° C. and a mold temperature of 150° C., to carry out tensile test, impact test, and thermal deformation test.
The results are shown in Table 1. Concerning tensile elongation and Izod impact strength, the maximum and minimum and mean values of samples are shown in Table 1. (Change in the amount of the component (C).)
As in the above Examples and Comparative Examples, using polyphenylene sulfide polymer and nylon 66 at the blend ratios shown in Table 2 (change in (A): (B)), tests were performed as in Examples 2 and 3, and Comparative Examples 2 and 3. The results are shown in Table 2.
As in the above Examples and Comparative Examples, using polyphenylene sulfide polymer and nylon 66 at the blend ratios shown in Table 3 (change in the amount of (D)), tests were performed as in Examples 2 and 3, and Comparative Examples 2 and 3. The results are shown in Table 3.
Replacing the nylon 66 in the Examples 2 and 3 and Comparative Examples 2 and 3 with nylon 6 or nylon 12, tests were performed at the blend ratios shown in Table 4, as in Examples 2 and 3, and Comparative Examples 2 and 3. The results are shown in Table 4.
Replacing the γ-aminopropyltriethoxysilane in Example 2 and Comparative Example 2 with γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, vinyltrimethoxysilane, and γ-diallylaminopropyltrimethoxysilane, tests were performed at the blend ratios shown in Table 5, as in Example 2 and Comparative Example 2. The results are shown in Table 5.
Replacing the water in Example 2 and Comparative Example 2 with benzyl alcohol, ethylene glycol, butanediol and glycerin, tests were performed at the blend ratios shown in Table 6, as in Example 2 and Comparative Example 2. The results are shown in Table 6.
Water was preliminarily added to or was made to humidify the powdery polyphenylene sulfide resin or nylon 66 described above at the ratios shown in Table 7, and blending was effected along with other components at the ratios shown in Table 7, which was then preliminarily mixed together with a Henschel mixer for five minutes. After the preliminary mixing, tests were performed as in Example 2. The results are shown in Table 7.
TABLE 1
__________________________________________________________________________
Comp. Ex. 1
Ex. 1
Comp. Ex. 2
Ex. 2
Comp. Ex. 3
Ex. 3
__________________________________________________________________________
Blend ratio
(A) polyphenylene sulfide resin (pts.
60 60 60 60 60 60
by wt.)
(B) nylon 66 resin (pts.
40 40 40 40 40 40
by wt.)
(C) γ-aminopropyltriethoxysilane (pts.
0.5 0.5
2.0 2.0
2.0 2.0
by wt.)
(D) water (in mole per one mole of (C))
-- 0.05
-- 0.05
-- 0.05
(E) glass fiber (pts. by wt)
-- -- -- -- 67 67
Physical properties of compositions
tensile strength (kgf/cm.sup.2)
778 782 845 852 2340 2350
tensile elongation
mean 30 34 48 52 5.7 6.1
(%) maximum
36 38 57 58 6.4 6.6
minimum
18 31 21 46 3.6 5.7
Izod impact strength notched
mean 3.4 3.6
5.0 5.3
12.4 12.9
(kgcm/cm) maximum
3.8 3.9
5.7 5.8
13.9 14.0
minimum
2.5 3.3
2.7 4.8
7.8 12.6
Izod impact strength unnotched
mean 48 53 80 85 52 57
(kgcm/cm) maximum
55 57 94 95 59 61
minimum
30 47 37 77 34 54
thermal deformation temperature [°C.],
110 110 108 108 254 254
18.6 kg load
__________________________________________________________________________
TABLE 2
__________________________________________________________________________
Comp. Comp. Comp. Comp.
Ex. 4
Ex. 4
Ex. 5
Ex. 5
Ex. 6
Ex. 6
Ex. 7
Ex. 7
__________________________________________________________________________
Blend ratio
(A) polyphenylene sulfide resin (pts.
80 80 40 40 80 80 40 40
by wt.)
(B) nylon 66 resin (pts. by wt.)
20 20 60 60 20 20 60 60
(C) γ-aminopropyltriethoxysilane (pts.
2.0
2.0
2.0
2.0
2.0
2.0
2.0
2.0
by wt.)
(D) water (in mole per one mole of (C))
-- 0.05
-- 0.05
-- 0.05
-- 0.05
(E) glass fiber (pts. by wt)
-- -- -- -- 67 67 67 67
Physical properties of compositions
tensile strength (kgf/cm.sup.2)
718 722 835 842 2010
2030 2335
2350
tensile elongation
mean 32 35 60 64 4.0
4.2
6.9
7.2
(%) maximum
37 39 69 70 4.7
4.8
8.0
8.1
minimum
21 32 32 57 2.4
3.8
3.1
6.5
Izod impact strength notched
mean 4.0
4.3
5.6
5.9
11.0
11.2
12.7
13.2
(kgcm/cm) maximum
4.6
4.7
6.5
6.6
12.2
12.3
14.1
14.3
minimum
2.5
3.9
3.0
5.1
6.8
10.5
8.2
12.0
Izod impact strength unnotched
mean 66 69 95 98 41 45 58 61
(kgcm/cm) maximum
77 78 110 114 47 49 65 66
minimum
35 62 47 88 31 42 39 57
thermal deformation temperature [°C.],
114 114 95 95 256 256 251 251
18.6 kg load
__________________________________________________________________________
TABLE 3
__________________________________________________________________________
Comp. Ex. 2
Ex. 2
Ex. 8
Ex. 9
Ex. 10
Comp. Ex. 3
Ex.
__________________________________________________________________________
11
Blend ratio
(A) polyphenylene sulfide resin (pts.
60 60 60 60 60 60 60
by wt.)
(B) nylon 66 resin (pts. by wt.)
40 40 40 40 40 40 40
(C) γ-aminopropyltriethoxysilane (pts.
2.0 2.0
2.0
2.0
2.0
2.0 2.0
by wt.)
(D) water (in mole per one mole of (C))
-- 0.05
0.5
1 3 -- 3
(E) glass fiber (pts. by wt)
-- -- -- -- -- 67 67
Physical properties of compositions
tensile strength (kgf/cm.sup.2)
845 852 852 851 848 2340 2345
tensile elongation
mean 48 52 52 54 56 5.7 6.3
(%) maximum
57 58 58 59 61 6.4 6.7
minimum
21 46 46 50 52 3.6 5.9
Izod impact strength notched
mean 5.0 5.3
5.3
5.5
5.6
12.4 13.0
(kgcm/cm) maximum
5.7 5.8
5.7
5.8
6.1
13.9 13.5
minimum
2.7 4.8
4.9
5.0
5.2
7.8 12.7
Izod impact strength unnotched
mean 80 85 85 86 88 52 59
(kgcm/cm) maximum
94 95 88 90 92 59 63
minimum
37 77 81 81 83 34 55
thermal deformation temperature [°C.],
108 108 108 108 107 254 254
18.6 kg load
__________________________________________________________________________
TABLE 4
__________________________________________________________________________
Comp. Comp. Comp. Comp.
Ex. 8
Ex. 12
Ex. 9
Ex. 13
Ex. 10
Ex. 14
Ex. 11
Ex. 15
__________________________________________________________________________
Blend ratio
(A) polyphenylene sulfide resin (pts.
60 60 60 60 60 60 60 60
by wt.)
(B)
nylon 6 resin (pts. by wt.)
40 40 -- -- 40 40 -- --
nylon 12 resin (pts. by wt.)
-- -- 40 40 -- -- 40 40
(C) γ-aminopropyltriethoxysilane (pts.
2 2 2 2 2 2 2 2
by wt.)
(D) water (in mole per one mole of (C))
-- 0.05
-- 0.05
-- 0.05
-- 0.05
(E) glass fiber (pts. by wt)
-- -- -- -- 67 67 67 67
Physical properties of compositions
tensile strength (kgf/cm.sup.2)
825 834 705 710 2100
2120 2000
2000
tensile elongation
mean 60 64 45 50 8.7
9.2
7.3
7.8
(%) maximum
69 70 56 58 9.4
9.8
8.5
8.7
minimum
35 56 20 44 5.6
8.5
3.6
7.0
Izod impact strength notched
mean 7.2
7.6
5.1
5.5
13.2
13.6
12.0
12.5
(kgcm/cm) maximum
8.0
8.3
5.9
6.1
14.5
14.7
13.3
13.5
minimum
3.9
7.0
2.8
5.0
8.9
12.4
7.9
11.6
Izod impact strength unnotched
mean 98 110 70 76 65 69 51 56
(kgcm/cm) maximum
113 121 83 85 73 75 59 61
minimum
51 101 40 66 46 61 35 47
thermal deformation temperature [°C.],
107 107 80 80 247 247 236 236
18.6 kg load
__________________________________________________________________________
TABLE 5
__________________________________________________________________________
Comp. Comp. Comp. Comp.
Ex. 12
Ex. 16
Ex. 13
Ex. 17
Ex. 14
Ex. 18
Ex. 15
Ex. 19
__________________________________________________________________________
Blend ratio
(A) polyphenylene sulfide resin (pts.
60 60 60 60 60 60 60 60
by wt.)
(B) nylon 66 resin (pts. by wt.)
40 40 40 40 40 40 40 40
(C)
γ-glycidoxypropyltrimethoxysilane
2 2 -- -- -- -- -- --
(pts. by wt.)
γ-mercaptopropyltrimethoxysilane
-- -- 2 2 -- -- -- --
(pts. by wt.)
vinyltrimethoxysilane (pts. by wt.)
-- -- -- -- 2 2 -- --
γ-diallylaminopropyltrimethoxy
-- -- -- -- -- -- 2 2
silane (pts. by wt.)
(D) water (in mole per one mole of (C))
-- 0.05
-- 0.05
-- 0.05
-- 0.05
(E) glass fiber (pts. by wt)
-- -- -- -- -- -- -- --
Physical properties of compositions
tensile strength (kgf/cm.sup.2)
865 875 810 820 825 835 840 845
tensile elongation
mean 54 58 42 45 46 49 47 50
(%) maximum
61 64 49 51 54 55 55 57
minimum
30 52 22 38 27 41 29 44
Izod impact strength notched
mean 6.0
6.3
4.5
4.8
4.8
5.2
4.9
5.2
(kgcm/cm) maximum
6.8
7.2
5.3
5.4
5.7
5.8
5.8
5.8
minimum
3.5
5.5
2.5
4.0
2.9
4.5
3.1
4.4
Izod impact strength unnotched
mean 95 100 70 74 75 79 78 82
(kgcm/cm) maximum
112 114 83 85 88 94 89 98
minimum
46 88 38 66 43 68 44 70
thermal deformation temperature [°C.],
107 107 109 109 108 108 108 108
18.6 kg load
__________________________________________________________________________
TABLE 6
__________________________________________________________________________
Comp. Ex. 2
Ex. 20
Ex. 21
Ex. 22
Ex. 23
__________________________________________________________________________
Blend ratio
(A) polyphenylene sulfide resin (parts
60 60 60 60 60
by wt.)
(B) nylon 66 resin (pts. by wt.)
40 40 40 40 40
(C) γ-aminopropyltriethoxysilane (pts.
2 2 2 2 2
by wt.)
(D)
benzylalcohol (in mole per one
-- 1.0
-- -- --
mole of (C))
ethylene glycol (in mole per one
-- -- 1.0
-- --
mole of (C))
butanediol (in mole to one mole
-- -- -- 1.0
--
of (C))
glycerine (in mole per one
-- -- -- -- 1.0
mole of (C))
(E) glass fiber (pts. by wt)
-- -- -- -- --
Physical properties of compositions
tensile strength (kgf/cm.sup.2)
845 850 853 853 854
tensile elongation
mean 48 51 53 52 54
(%) maximum
57 57 59 60 59
minimum
21 40 48 47 50
Izod impact strength notched
mean 5.0 5.1
5.4
5.4
5.6
(kgcm/cm) maximum
5.7 5.6
5.8
5.9
6.0
minimum
2.7 4.1
4.8
4.9
5.1
Izod impact strength unnotched
mean 80 83 85 85 86
(kgcm/cm) maximum
94 94 96 97 100
minimum
37 60 78 77 80
thermal deformation temperature [°C.],
108 108 108 108 108
18.6 kg load
__________________________________________________________________________
TABLE 7
__________________________________________________________________________
Comp. Ex. 2
Ex. 24
Ex. 25
Ex. 3
__________________________________________________________________________
Blend ratio
(A) polyphenylene sulfide resin (parts
60 60 60 60
by weight)
(B) nylon 66 resin (pts. by wt.)
40 40 40 40
(C) γ-aminopropyltriethoxysilane (pts.
2 2 2 2
by wt.)
(D)
water added to (A) (in mole per
-- 0.5
-- --
one mole of (C))
water added to (B) (in mole per
-- -- 0.5
--
one mole of (C))
water added to (C) (in mole per
-- -- -- 0.5
one mole of (C))
(E) glass fiber (pts. by wt)
-- -- -- --
Physical properties of compositions
tensile strength (kgf/cm.sup.2)
845 851 852 852
tensile elongation
mean 48 50 51 52
(%) maximum
57 57 59 58
minimum
21 40 45 46
Izod impact strength notched
mean 5.0 5.2
5.3
5.3
(kgcm/cm) maximum
5.7 5.8
5.7
5.7
minimum
2.7 4.1
4.7
4.9
Izod impact strength unnotched
mean 80 85 84 85
(kgcm/cm) maximum
94 91 90 88
minimum
37 74 80 81
thermal deformation temperature [°C.],
108 108 108 108
18.6 kg load
__________________________________________________________________________
Claims (20)
1. A method of preparing a polyarylene sulfide resin composition, comprising; forming a mixture of the following components:
(A) 97 to 20 parts by weight of a polyarylene sulfide resin and
(B) 3 to 80 parts by weight of a polyamide resin, with
(C) 0.01 to 5 parts by weight of at least one silane compound selected from the group consisting of vinylalkoxysilane, epoxyalkoxysilane, aminoalkoxysilane, mercaptoalkoxysilane and allylalkoxysilane, and
(D) 0.03 to 5 moles per mole of said silane compound (C) of water or at least one alcohol having a boiling point of 100° C. or more, and heat melting and kneading said mixture for 30 seconds or more.
2. The method of claim 1 wherein said component (D) is said at least one alcohol each having at least two hydroxyl groups.
3. The method of claim 1 wherein said polyarylene sulfide resin (A) comprises polyphenylene sulfide.
4. The method of claim 3 wherein said polyphenylene sulfide comprises a homopolymer composed of p-phenylene sulfide groups.
5. The method of claim 3 wherein said polyphenylene sulfide comprises a copolymer composed p-phenylene sulfide groups and m-phenylene sulfide groups.
6. The method of claim 5 wherein said copolymer comprises 5 to 40 mole % of said m-phenylene sulfide groups and 60 to 95 mole % of said p-phenylene sulfide groups.
7. The method of claim 1 wherein said polyamide resin (B) is selected from nylon 6, nylon 66, nylon 12 and copolymers thereof.
8. The method of claim 1 wherein said component (D) is water.
9. The method of claim 1 wherein said mixture is formed by mixing component (D) with said one silane compound (C) and adding the mixture of (C) and (D) to a mixture of said polyarylene sulfide resin (A) and said polyamide resin (B) prior to said heat melting and kneading.
10. The method of claim 1 wherein said mixture is formed by mixing said component (D) with said polyarylene sulfide resin (A), said polyamide resin (B) or a mixture of (A) and (B) prior to mixing with said component (C).
11. The method of claim 10 wherein said component (D) is water.
12. The method of claim 5 further mixing (E) 1 to 400 parts by weight of at least one filler with said mixture.
13. The method of claim 12 wherein said filler (E) comprises a fibrous, powdery or flaky filler.
14. The method of claim 13 wherein said filler comprises glass or carbon fiber.
15. The method of claim 13 wherein said filler comprises a mixture of a fibrous filler with a powdery or flaky filler.
16. A polyarylene sulfide resin composition prepared by the method of claims 1 or 2.
17. The polyarylene sulfide resin composition of claim 16 further including 1 to 400 parts by weight of a filler (E).
18. The polyarylene sulfide resin composition of claim 17 wherein said filler comprises a fibrous, powdery or flaky filler.
19. The polyarylene sulfide resin composition of claim 17 wherein said filler (E) comprises glass or carbon fiber.
20. The polyarylene sulfide resin composition of claim 16 wherein said polyarylene sulfide is selected from a homopolymer composed of p-phenylene sulfide units or a copolymer composed of a mixture of p-phenylene sulfide units and m-phenylene sulfide units.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2220774A JP2683442B2 (en) | 1990-08-21 | 1990-08-21 | Polyarylene sulfide resin composition and method for producing the same |
| JP2-220774 | 1990-08-21 |
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| Publication Number | Publication Date |
|---|---|
| US5262461A true US5262461A (en) | 1993-11-16 |
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|---|---|---|---|
| US07/856,148 Expired - Lifetime US5262461A (en) | 1990-08-21 | 1991-08-15 | Polyarylene sulfide resin composition and method for preparing the same |
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| Country | Link |
|---|---|
| US (1) | US5262461A (en) |
| JP (1) | JP2683442B2 (en) |
| CA (1) | CA2066682A1 (en) |
| WO (1) | WO1992003508A1 (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999020692A1 (en) * | 1997-10-23 | 1999-04-29 | University Of Florida | Bioactive composites comprising silane functionalized polyaryl polymers |
| US20020149493A1 (en) * | 2001-03-30 | 2002-10-17 | Yukihiko Yudate | Paved-road-embeddable information transmitting/receiving apparatus |
| EP0757265B1 (en) * | 1995-08-02 | 2003-11-19 | Ems-Inventa Ag | Polymer sheath for optical waveguides |
| US20050008620A1 (en) * | 2002-10-08 | 2005-01-13 | Shimp Lawrence A. | Coupling agents for orthopedic biomaterials |
| US20050008672A1 (en) * | 2002-12-12 | 2005-01-13 | John Winterbottom | Formable and settable polymer bone composite and method of production thereof |
| US8012210B2 (en) | 2004-01-16 | 2011-09-06 | Warsaw Orthopedic, Inc. | Implant frames for use with settable materials and related methods of use |
| US9034356B2 (en) | 2006-01-19 | 2015-05-19 | Warsaw Orthopedic, Inc. | Porous osteoimplant |
| US9107751B2 (en) | 2002-12-12 | 2015-08-18 | Warsaw Orthopedic, Inc. | Injectable and moldable bone substitute materials |
| CN115066459A (en) * | 2020-02-10 | 2022-09-16 | 宝理塑料株式会社 | Method for producing polyarylene sulfide resin composition |
| CN115181424A (en) * | 2022-09-15 | 2022-10-14 | 广州辰东新材料有限公司 | Polyphenylene sulfide composite material for nano injection molding and preparation and application thereof |
| CN116285336A (en) * | 2023-04-06 | 2023-06-23 | 济南际通智能制造有限公司 | Long-term cold-resistant ribbon material and preparation method thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015010158A (en) * | 2013-06-28 | 2015-01-19 | Dic株式会社 | Polyarylene sulfide resin composition, molded article, and production method thereof |
| WO2021161995A1 (en) * | 2020-02-10 | 2021-08-19 | ポリプラスチックス株式会社 | Polyarylene sulfide resin composition production method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5070127A (en) * | 1989-07-07 | 1991-12-03 | Hoechst Celanese Corporation | Impact modified polyphenylene sulfide |
| US5070151A (en) * | 1989-04-18 | 1991-12-03 | Sumitomo Chemical Co., Ltd. | Resin composition |
| US5149731A (en) * | 1990-04-25 | 1992-09-22 | Polyplastics Co., Ltd. | Polyarylene sulfide resin composition |
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| JPS5252958A (en) * | 1975-10-23 | 1977-04-28 | Mitsubishi Rayon Co Ltd | Glass-fiber reinforced polyphenylene sulfide resin compositions |
| JPS591422B2 (en) * | 1976-12-03 | 1984-01-12 | 保土谷化学工業株式会社 | Polyphenylene sulfide resin composition |
| JPS5529526A (en) * | 1978-08-21 | 1980-03-01 | Shin Etsu Chem Co Ltd | Polyphenylene sulfide resin composition |
| JPH0639113B2 (en) * | 1987-09-02 | 1994-05-25 | ポリプラスチックス株式会社 | Polyarylene sulfide resin molded product having welded portion |
| JP2608068B2 (en) * | 1987-09-30 | 1997-05-07 | ポリプラスチックス株式会社 | connector |
| JPH0651311B2 (en) * | 1987-08-03 | 1994-07-06 | ポリプラスチックス株式会社 | Polyarylene sulfide resin molded product having welded portion |
| JPH01146955A (en) * | 1987-12-03 | 1989-06-08 | Kureha Chem Ind Co Ltd | Polyphenylene sulfide resin composition and its production |
| JPH07107133B2 (en) * | 1988-11-30 | 1995-11-15 | ポリプラスチックス株式会社 | Polyarylene sulfide resin composition |
-
1990
- 1990-08-21 JP JP2220774A patent/JP2683442B2/en not_active Expired - Lifetime
-
1991
- 1991-08-15 US US07/856,148 patent/US5262461A/en not_active Expired - Lifetime
- 1991-08-15 CA CA002066682A patent/CA2066682A1/en not_active Abandoned
- 1991-08-15 WO PCT/JP1991/001090 patent/WO1992003508A1/en not_active Ceased
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5070151A (en) * | 1989-04-18 | 1991-12-03 | Sumitomo Chemical Co., Ltd. | Resin composition |
| US5070127A (en) * | 1989-07-07 | 1991-12-03 | Hoechst Celanese Corporation | Impact modified polyphenylene sulfide |
| US5149731A (en) * | 1990-04-25 | 1992-09-22 | Polyplastics Co., Ltd. | Polyarylene sulfide resin composition |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0757265B1 (en) * | 1995-08-02 | 2003-11-19 | Ems-Inventa Ag | Polymer sheath for optical waveguides |
| US6399693B1 (en) | 1997-10-23 | 2002-06-04 | Univ. Of Florida Research Foundation | Bioactive composites comprising silane functionalized polyaryl polymers |
| WO1999020692A1 (en) * | 1997-10-23 | 1999-04-29 | University Of Florida | Bioactive composites comprising silane functionalized polyaryl polymers |
| US20020149493A1 (en) * | 2001-03-30 | 2002-10-17 | Yukihiko Yudate | Paved-road-embeddable information transmitting/receiving apparatus |
| US8686064B2 (en) | 2002-10-08 | 2014-04-01 | Warsaw Orthopedic, Inc. | Coupling agents for orthopedic biomaterials |
| US20050008620A1 (en) * | 2002-10-08 | 2005-01-13 | Shimp Lawrence A. | Coupling agents for orthopedic biomaterials |
| US7270813B2 (en) | 2002-10-08 | 2007-09-18 | Osteotech, Inc. | Coupling agents for orthopedic biomaterials |
| US20050008672A1 (en) * | 2002-12-12 | 2005-01-13 | John Winterbottom | Formable and settable polymer bone composite and method of production thereof |
| US10080661B2 (en) | 2002-12-12 | 2018-09-25 | Warsaw Orthopedic, Inc. | Injectable and moldable bone substitute materials |
| US7291345B2 (en) | 2002-12-12 | 2007-11-06 | Osteotech, Inc. | Formable and settable polymer bone composite and method of production thereof |
| US20080063684A1 (en) * | 2002-12-12 | 2008-03-13 | John Winterbottom | Formable and Settable Polymer Bone Composite and Methods of Production Thereof |
| US9107751B2 (en) | 2002-12-12 | 2015-08-18 | Warsaw Orthopedic, Inc. | Injectable and moldable bone substitute materials |
| US9308292B2 (en) | 2002-12-12 | 2016-04-12 | Warsaw Orthopedic, Inc. | Formable and settable polymer bone composite and methods of production thereof |
| US9333080B2 (en) | 2002-12-12 | 2016-05-10 | Warsaw Orthopedic, Inc. | Injectable and moldable bone substitute materials |
| US8012210B2 (en) | 2004-01-16 | 2011-09-06 | Warsaw Orthopedic, Inc. | Implant frames for use with settable materials and related methods of use |
| US9034356B2 (en) | 2006-01-19 | 2015-05-19 | Warsaw Orthopedic, Inc. | Porous osteoimplant |
| CN115066459A (en) * | 2020-02-10 | 2022-09-16 | 宝理塑料株式会社 | Method for producing polyarylene sulfide resin composition |
| CN115066459B (en) * | 2020-02-10 | 2023-02-28 | 宝理塑料株式会社 | Method for producing polyarylene sulfide resin composition |
| CN115181424A (en) * | 2022-09-15 | 2022-10-14 | 广州辰东新材料有限公司 | Polyphenylene sulfide composite material for nano injection molding and preparation and application thereof |
| CN115181424B (en) * | 2022-09-15 | 2022-11-18 | 广州辰东新材料有限公司 | Polyphenylene sulfide composite material for nano injection molding and preparation and application thereof |
| CN116285336A (en) * | 2023-04-06 | 2023-06-23 | 济南际通智能制造有限公司 | Long-term cold-resistant ribbon material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CA2066682A1 (en) | 1992-02-22 |
| WO1992003508A1 (en) | 1992-03-05 |
| JP2683442B2 (en) | 1997-11-26 |
| JPH04100860A (en) | 1992-04-02 |
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